Calculation of Raman Optical Activity Spectra of Methyl-β-d -Glucose Incorporating a Full Molecular Dynamics Simulation of Hydration Effects
Autor: | Ewan W. Blanch, James R. Cheeseman, Majeed S. Shaik, Paul L. A. Popelier |
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Rok vydání: | 2011 |
Předmět: |
Chemistry
Molecular Conformation Solvation General Chemistry Molecular Dynamics Simulation Spectrum Analysis Raman Biochemistry Polarizable continuum model Catalysis symbols.namesake Molecular dynamics Glucose Colloid and Surface Chemistry Chemical physics Ab initio quantum chemistry methods Molecular vibration symbols Physical chemistry Density functional theory Raman optical activity Physics::Chemical Physics Raman spectroscopy |
Zdroj: | Journal of the American Chemical Society. 133:4991-4997 |
ISSN: | 1520-5126 0002-7863 |
Popis: | We report calculations of the Raman and Raman optical activity (ROA) spectra of methyl-β-D-glucose utilizing density functional theory combined with molecular dynamics (MD) simulations to provide an explicit hydration environment. This is the first report of such combination of MD simulations with ROA ab initio calculations. We achieve a significant improvement in accuracy over the more commonly used gas phase and polarizable continuum model (PCM) approaches, resulting in an excellent level of agreement with the experimental spectrum. Modeling the ROA spectra of carbohydrates has until now proven a notoriously difficult challenge due to their sensitivity to the effects of hydration on the molecular vibrations involving each of the chiral centers. The details of the ROA spectrum of methyl-β-D-glucose are found to be highly sensitive to solvation effects, and these are correctly predicted for the first time including those originating from the highly sensitive low frequency vibrational modes. This work shows that a thorough consideration of the role of water is pivotal for understanding the vibrational structure of carbohydrates and presents a new and powerful tool for characterizing carbohydrate structure and conformational dynamics in solution. |
Databáze: | OpenAIRE |
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